A series of novel charged disilver(I) complexes with pyridyl-containing phospholanes was synthesized. These complexes were characterized using a range of spectroscopic techniques and single-crystal and powder X-ray diffraction. The complexes demonstrate solid-state near-infrared (NIR) luminescence (765-902 nm) that is unique for dinuclear Ag ^I complexes. Combined spectroscopic/quantum chemical analysis suggests that the NIR luminescence of complexes 4-6 in the solid state is mainly due to crystal packing effects.